PREPARATION  OF  MERGURATED 
TOLYL-FURFURANES 


BY 

HARRY  FRANCIS  WATSON 


THESIS 

FOR  THE 

DEGRE  E O F B AGH  ELOR  OF  SCIENCE 


IN 

CHEMISTRY 


GOELEGE  OF  LIBERAL  ARTS  AND  SCIENCES 

UNIVERSITY  OF  ILLINOIS 


1922 


/922 

VV333 


UNIVERSITY  OF  ILLINOIS 


Mfty_ 3^ 192^ 


THIS  IS  TO  CERTIFY  THAT  THE  THESIS  PREPARED  UNDER  MY  SUPERVISION  BY 

Harry  Francia  Watson 


ENTITLED ® 


IS  APPROVED  BY  ME  AS  FULFILLING  THIS  PART  OF  THE  REQUIREMENTS  FOR  THE 
DEGREE  OF 

in  Chemistry 


Approved 


bi'.A-k 


HEAD  OF  DEPARTMENT  OF 


600254 


Digitized  by  the  Internet  Archive 
in  2016 


https://archive.org/details/preparationofmerOOwats 


AcknowledR-ement 

The  preparation  of  the  raer curated 
allyl  cresols  v;as  undertaken  at  the  suggestion 
of  Dr.  Roger  Adams.  I wish  to  express  my  thanks 
for  the  kindly  help  and  suggestions  of  Dr.  Adams 
hy  means  of  which  the  work  ?;as  conducted. 


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The  Preparation  of  Llercurated  Tolyl  furfuranes* 

by  H.  k'/atson 


Table  of  Contents 

Page 

History,  Bibliography  and 

Theoretical  Considerations 
of  the  Organic  Ilercury 

Compounds 1-4 

Experimental  5-13 

Conclusion 14 


History  and  Biblio^2:raph.7  of  the  0r:5:anic  Hercury  Oompounds* 

The  first  organic  mercary  compound  v/as  obtained 

by  A.u'.Eofman  in  1845  from  the  interaction  of  mercuric 

chloride  and  aniline.  In  1850  I’ranlcland  obtained  GH^Hgl 

o 

by  the  reaction  between  ethyl  iodide  and  merciu-y.  In  1855 

Zinn  discovered  the  mercurated  allyl  compounds,  which 

he  made  by  the  reaction  between  allyl  iodide  and  mercury; 

giving  GH2=GK-GH  Kgl*  Tlie  general  method  for  the  prep- 

aration  of  organic  mercury  compounds  was  discovered  by 

Franhland  in  1865:  the  sodium  amalgam  is  treated  v/ith 

allcyl  iodide  in  ethyl  acetate  solution;  the  di  alkyl 

mercuiy  compound  is  formed  as  shov/n  2GH  I HgSITa 

5 

21IaI  GHrz-Hg-GHr. . In  1880  Zutscheroff  made  the  first 
o o 

systematic  study  of  the  action  of  mercury  salts  on  allyl- 
ene  and  aceytlene;  however  the  stru.cture  of  the  triple 
bond  mercurated  compounds  is  still  in  doubt.  It  was 
tiiDUght  the  work  of  Bilboni  and  Paolini  that  the  mercury 
derivatives  of  the  allyl  phenyl  ethers  v;ere  first  isol- 
ated and  studied. 


Bibliography 

The  references  consulted  in  the  historical  and  theo- 
retical discussion  are  ’.Thitman’s  Organic  Compounds  of 
Hercury,  pp. ( 15-40) ,( 284-286) ; Bilboni  and  Paolini,  Berichte- 


-2- 


£994-2998,  Berich1:e  3575. 

Ivlanchot:-  Annelen  der  Ghemie  420,  pp.  170-176;  421,  366-569. 

Theoretical  Discussion. 

A general"  method  for  the  preparation  of  organic  mercury 
compounds  from  an  unsaturated  aliphatic  is  the  treatment 
of  the  compound  v.ith  a mercuric  salt  in  aqueous  or  alcoholic 
solution^  The  general  reaction  is  an  addition  of  Hg  and 
OH  to  the  double  bond  in  aqueous  and  an  Hg  and  OCH^  in 

k) 

methyl  alcohol  solution.  The  addition  compounds  of-. ethyl- 
ene have  been  the  most  studied,  the  general  reaction  being: 

CHgsGHg  2HgXg  HgO  XHg-GHg-CHg-OH 

2CH^=GH^  SHgXg  HgO  XHg-GHg-GHg-OzGHg-CHgEgX  HX 

The  proof  of  the  stucture  of  the  mer curated  ethylene 
compounds  rests  upon  the  ease  Vidth  which  ethyl  alcohol 
may  be  formed  from  the  first  compound,  and  di-iododiethyl 
ether  from  the  second.  Opposed  to  this  belief  in  the 
stiucture  given  is  the  molecular  formula  BG^H^HgOHgX^  and 
GgH^HgfOH).  Ilanchot  inclines  to  the  molecular  structure, 
basing  his  conclusion  on  the  esse  with  v/hich  the  compounds 
are  broken  dovm  with  dilute  HGl,  giving  OgH^  quantitatively 
when  an  alcohol  would  be  the  natural  expectation  if  an 
addition  compound  is  formed. 


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The  mercury  compounds  of  the  allyl  phenyl  ethers 
formed  from  mercuric  salts  are  thought  by  ivlanchot  to 
give  t\vo  compounds,  either  isomeric  or  polymers  (Annalen 
421 , 316-520).  luanchot  inclines  to;vard  the  belief  of  a 
rnolecul  or  compound  and  not  an  addition,  basing  his  belief 
on  the  ease  of  hydrolysis  with  HOI  to  give  the  original 
allyl  phenyl  ether  and  HgOl.  He  attempts  no  explanation 
of  the  inertness  of  the  mercury  toward  HaOH  or 


vHiitman  considers  that  it  is  probable  that  one  of 
the  compounds  maybe  molecular,  the  other  an  addition 
product. 


Hr.  Adams  suggested  that  the  cresols  v/ould  probably 
form  mer curated  furfuranes  similar  to  those  formed  from 
the  phenols. 

The  reaction  is  probably  as  shovm: 


ITI4OH 


Purpose  of  the  .experimental  iiYorIc 


OH 


OH  Cl 


GHgsxGH-Ghg  HgGl 


GH^zGH-GHgHgGl 


■5 


0 


GH£-GH-GHHgGl 


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GKg-GH-GE  EgCl 

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The  general  reaction  with  compoimds  of  the  type 
H-GE^sCEg  is  EGEg-  GE£  R-GSg-GSg  EGl 
G1  EgGl  OE  EgGl 

The  research  was  undertaken  in  order  to  prepare 
mercurated  furfuranes  from  the  cresois  similarly  to  those 
prepared  from  the  phenols. 


-5- 


Zxperimental  i/Vork 

Allyl  bromide  was  prepared  according  to  t2ie  method 
given  in  "Organic  Chemical  Heagents"  vol.  I. 

The  allyl  para-cresol  ether  was  prepared  accoring  to 
method  given  by  L.  Glaisen( Annalen  der  Ghemie,  401,  21-119. 
The  distilled  ether  was  rearranged  to  allyl  papa  cresol 
according  to  the  method  of  Glaisen^as  cited-  The  material 
v/as  distilled  at  20  mm.  pressure,  dissolved  in  lO^b  haOH, 
the  alheline  solution  washed  twice  with  petroleum  ether, 
the  cresol  precipitated  with  HGl,  and  extracted  v/ith 
petroletima  ether,  and  the  petroleum  ether  driven  off. 

Yield  of  purified  material  64  grams  from  100  grams  of 
para  cresol.  Yield  46,'o. 

Ireparation  of  the  Tolyl  Mercurated  IPurfurane. 

I’ive  grams  of  the  l-methyl-S-allyl-4-hydroxybenzene 
was  added  to  9.2  grams  of  HgGl^  dissolved  in  250  c.c.  of 
water.  Hapid  mechanical  agitation  was  used  for  four  hours 
and  then  stood  over  night.  Yield  10.1  grams  of  dry  gran- 
ular material.  The  material  was  crystalized  from  hot 
alcohol  three  times,  clean  crystals  were  obtained.  Yield 
of  crystals  6 grams.  M.l.  99.0^-99.5^^.  mother  liquor 
gave  no  syrup- like  bodies. 

A second  lot  was  similarly  prepared;  yield  6.6  grams 
II.  1.  99*0^.09,50^ 


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The  first  sample  was  analyzed  for  Cl  and  Eg. 

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o 


Molecular  Wt.  of 


Theoretical  Chlorine 


GE  CH-GE  HgCl 
S 2 ^ 

0 

9.23^ 


is  382.5 


Determination  I 

Determination  II 

Weight  of  Gooch  and  AgGl 

22.7702 

22.9618 

’ ' ” ” alone 

22.5760 

22.7706 

" ” AgCl 

.1942 

.1916 

Blanh  on  reagents  .0093 

Corrected  wt.  of  AgCl  .1849 


.0093 


.1823 


^649„_x  ,2474.  . ^ _il823  . g ..2474  = q.qsjJ  Cl 


The  chlorine  v;as  determined  by  fusion  in  EagOgbomb. 


The  EggGlg  formed  reduced  with  Zh  E^SO^,  the  Zn  removed 
by  boiling  Ea^GOg  solution  and  Cl  determined  in  Usual  manner 
by  gravimetric  AgEO^.  The  blank  found  on  Ej,g02  used  .1  gram 
benzoic  acid  and  EEQ^. 

The  Eg  v/as  obtained  by  hydrolysis  v/ith  1-1  EGl  by 
refluxing  and  washing  the  allyl  cresol  with  water,  and  repeating 
the  hydrolysis  and  extraction.  The  method  was  a modification 
of  the  one  used  by  Manchot  ( Annalen  421,  page  420).  The 
EaCE  and  AgEO^  method  of  analysis  was  used. 


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CH, 


Mercury  in 


CHg-OE-GHgiigGl 


Stock  solution  ITaCn,  12  grams  to  500  c.c.  of  H O 
125  c.c.  of  stock  to  100  c.c.  for  standard  solution. 

Standard  used  HgGl  crys tallyzed  from  HpO  twice,  once  from 
absolute  alcohol  and  dried  at  110^;  .5  grams  of  HgCl^  titrat- 
ed with  ITaGn. 

AgHOg  solution  3 grams  to  600  c.c. 


Standardization 
.5  gram  EgGl^  .2691  of  Eg. 

70.71  of  NaOn  used  against  .3691  Eg. 
1 c.c.  .00522  Eg 

1 c.c.  of  AgEOg  1.44  EaCii 
80  c.c.  of  EaOn  used. 

Back  titration  AgMOg  6.96  c.c. 

EaGH  used  by  Eg  70.71 


.5  of 


CH^-GE-GH  EgGl 

0 


Eg  Theoretical 


70  c.c 


14.05 


49.71 

49.71 


. of  EaGE  used 

of  AgEO,-  used  for  back  titration 
c.c.  of  EaGE  used  by  Eg. 


X .00522  . 


51.91  ^ Eg  found. 


52.28?^ 


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-8- 


Preparation  of  ortho  Cresol 
The  raaterial  was  r^ade  in  a similar  manner  to  the  ptra 
compound;  and  it  was  purified  in  a similar  manner. 

Yield  83  grams  from  100  of  ortho  cresol. 

Per  cent  yield  63  io* 

Preparation  of  the  Ortho  Tolyl 

Mercurous  chloride  Purfurane 

E'ive  grams  of  1-methyl- £-hydroxy-3-allyl-henzene  was 
added  to  9.2  grams  of  HgOlg  dissolved  in  250  c.c.  of  KgO. 
Rapid  mechanical  agitation  was  used  for  seven  hours.  An. 
oily  serai  solid  "body  resell  ted  which  was  dried  over  CaClg. 
The  material  was  purified  by  washing  with  ice  cold  ether, 
and  drying  the  amorphous  powder  which  resulted. 

The  powder  was  crystallized  three  times  from  absolute 
alcohol. 

Yield  of  crystals  6.2  grams.  II. P.  88°-89° 

Analytical  Data 


.5  gram  of 

OHg-CK-CHgEgCl 

Theoretical  Hg  52.28/^ 

1 c.c.  of  Standard  ITaCN  .00522  gm.  of  Hg 

1 c.c.  of  AgllOg  1.44  of  llaCH 

55.0  c.c.  of  llaOlT 

5.1  c.c.  of  AgliOg  back  titration 


-9- 


IJaCU  used  to  titrate  Kg  48.i54 


48.34  X .005££ 

6 - 

55  c.c,  of  IlaOK 

4*£V  c*c.  of  AgKOg 

FaOlT  to  titrate  Hg 

48.84  X .005££ 

5 ' 

Molecular  weight 


50.46  io  Hg 
■Determination  II 

48.84 

50.98  io  Hg 
^ 0 

CH2-GH-CH2HgCl 


38£.5 


Preparation  of  Alljl  Organic  Mercurous  Sulphates  from 

the  Allyl  Qresols 

Pive  grams  of  1-me  thy  1-3-ally l-4-hydroxy-'beniiene  was 
added  to  10  grams  of  HgSO^  dissolved  in  £50  c.c.  of  8 ^ 
HgSO^.  The  mixture  was  stirred  for  seven  hours.  The 
material  formed  was  granular  and  Vv’hite;  it  ?/as  v/ashed  and 
dried.  It  v/eighed  14  grams,  and  proved  insoluble  in  H^O, 
GHgOH,  GgHgOH,  GH^GOGHg,  GHgCHgCEgGH^OH  and  GH^GOgH. 

Ho  criterion  of  purity  w'-as  taken. 

The  Preparation  of  Allyl  Organic  Mercurous  Sulphates  from 

the  Allyl  Gresols. 

Pive  grams  of  l-methyl-£-hydroxy-3-allyl  benzene  was 
stirred  with  10  grams  of  HgSO^  dissolved  in  £50  c.c.  of 


■!  f > f 

•,1 


•l 


(. 

K 

I 

»' 


ti 


-10- 


8/0  material  v;as  stirred  for  6 hours;  it  vms  a 

■blach  gummy  mass.  The  gurae  like  material  was  washed  vd.th 
ether  and  a slate  colored  powder  was  obtained. 

Yield  3.0  grams. 


Preparation  of  the  Ally  Organic  Merouous  Acetates  from 

The  Ally  Oresols 

Seven  grams  of  GH  and  15.1  grams  of 

OH 

GH^-GH-GHg 

Hg(Ac)^  were  agitated  in  200  c.c.  of  S GHgOOgH  for  4 
hours-  A pinkish  lAhite  pov/der  resulted.  Dry  v/eight  16 
grams.  It  dissolved  in  alcohol  to  a syrup;  the  alcohol 
removed  by  blowing  air  over  the  surface  of  the  solution 
( Boiling  caused  hydrolysis).  The  semi  crystalline  material 
obtained  was  washed  with  ice  cold-aether;  an  amorphous 
powder  being  left.  This  was  crystallised  from  alcohol  at 
-10°.  Weight  6.2  grams.  i/I.P.  109®  - 110.5®. 

The  wash  ether  gave  a residue  of  3.3grams  of  syrup- like 
material . 


Molecular  Wt.  of 


Analytical  Data 


GE^-GK-CH2HgAc  (?)  » 396 

Theoretical  Hg  = 50.50  °Jo 

Hydrolysed  v/ith  dilute  EGl  method  followed  identical  with 
previous  determina tions.  V<eight  of  saiipl e hydrolysed  .5  gram. 


-11- 


Nev/  Standardization  of  ITaCIT 

80  c.o.  of  NaGN  talcen,.5  gram  of  HgOl^  for  standard. 
Back  titration  4.22  AgilO^*  1 c.c.  AgNO^  - 1.50-..lia0B 
NaGN  used  titrate  .3691  gram  Hg  = 73.67 


p— = .00501 
7o . o7 


1 c.c.  of  NaClI  = ,00501  Eg 

GH^ 

^ 0 


Mercury  in 


GEg-GH-GHgKgAc  C?j 


Molecular  Jt.  = 596 
Theoretical  Hg  = 50.50  io 


determination  I 


55  c.c.  of  NaGE  taken 


Back  titration  7.00  c.c.  of  AgEO^, 

o 


EaGE  used  = 44.50 

44i50  X .00501 

.5 


= 44.60  io 


determination  II 


55  c.c.  of  EaGE  taken 
Back  titration  6.80  c.c.  AgEO^ 
EaGE  used  for  Eg  = 44.80  c.c. 
44.80  X .00501  ^ ^ no  .-y 

“p.  S • OO  jO 

• D 


Her  cent  Hg.  found  in  crystalline  material  44.60  fo. 


frtuv  "'c- ‘ i* , -i  ■ ^ uu, 


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The  Preparation  of  the  Allyl  Organic  I.'Iorcuous  Acetate  from 

All.yl  para-QresoI 

Seven  grams  of  1- me thy 1-3- ally 1-4- hydroxy  benzene  was 
stirred  in  tlie  same  concen  tration  of  Hg(ii.c)  as  in  the  prev- 
ious experiment.  A sticky  semi-solid  resulted,  that  v/as 
removed  from  the  flask  by  dissolving  in  alcohol.  The  alcohol 
was  evaporated  off  at  45°  by  a current  of  air;  the  material 
obtained,  11  grams,  v/as  washed  twice  with  ether  at  0°;  then 
dissolved  in  alcohol  from  v/lich  it  could  not  be  removed  by 
chilling.  The  alcohol  was  again  evaporated  by  a current  of 
air,  and  the  material  washed  v/ith  ether,  v/hen  taken  into 
solution  in  alcohol  and  chilled  to  -10°  a semi-ci^'stalline 
mass  v/as  obtained. 

Yield  £.82  grams.  Ll.ir.  149°  - 150°. 

rrepai^tion  of  the  Iodides  from  the  Acetates 

\- 

Three  grams  of  allyl  orthocresol  mercurous  acetate 
compound  was  treated  with  1.3  grams  of  ICE,  the  mixture  v/as 
shaken  for  three  hours  and  allowed  to  stand  for  tun  days. 

The  material  v/as  obtained  as  a granular  body.  The  material 
proved  very  soluble  in  alcohol;  E parts  of  the  solid  dissolv- 
ing in  one  of  alcohol.  It  was  purified  by  successive  ether 
washings  and  alcohol  purifications. 

Yield  of  serni^  ciy^stalline  powder  3 grams. 

LI.P.  65°  - 69°. 


-13- 


Preparation  of  the  Iodides  form  the  Acetates 

One  and  forty-six  hundredths  grams  of  ally!  para-oresol 
mercurous  acetate  Vvas  shahen  vAth  .6  gram  of  hi  in  50c. c. 
of  HgO  for  three  hours  and  allowed  to  stand  for  2 day  s- 
A gummy  material  was  formed.  It  v/as  v/ashed  repeatedly  with 
ether;  the  residue  was  an  amorphous  powder,  which  v/as  very 
slightly  soluble  in  alcohol  or  ether. 

Yield  .7  gram.  M.r.  108°  - 110° 


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-14- 


GOHGLUSIOIT 


The  vvork  done  has  shOvvn  ttiat  organic  mercury 
compounds  are  formed  from  the  allyl  cresols  as  from 
the  allyl  phenols.  The  purification  of  the  acetates, 
and  iodides  from  from  them,  is  difficult,  by  reason  of 
the  nature  of  the  material,  and  the  lov/  yield  of  semi- 
crystalline powder  obtained. 


